Microstructure and wear resistance of electrodeposited Ni-SiO2

nano-composite coatings on AZ91HP magnesium alloy substrate

LIU Yan1, YU Si-rong2, LIU Jin-dan1, HAN Zhi-wu1, YUAN Dong-sheng2

1. Key Laboratory for Bionic Engineering, Ministry of Education, Jilin University, Changchun 130022, China;
2. College of Materials Science and Engineering, Jilin University, Changchun 130022, China
Received 10 May 2011; accepted 25 July 2011

Abstract: The Ni-SiO2 nano-composite coatings were fabricated by electrodeposition on the AZ91HP magnesium alloy surface, in
which nano-SiO2 was chosen as the second-phase particulates. The microstructure was observed by SEM, the microhardness was
measured by micro-density tester and the wear resistance was estimated by M−200 type block-on-wheel dry sliding frication and
wear tester. The results indicate that the Ni-SiO2 nano-composite coatings with uniform crystalline, dense structure can be obtained
on AZ91HP magnesium alloy. The interface morphology shows that the combination between the nano-composite coatings and
magnesium alloy is fine. The maximum value of microhardness reaches HV367 when the content of nanoparticles is 10 g/L, however,
the microhardness of the pure nickel coatings is HV274 and the hardness of magnesium alloy only is HV82.7. The frication and wear
experiments reveal that the wear resistance of nano-composite coatings are improved obviously compared to magnesium alloys and
pure nickel coatings, which are induced by dispersive strengthening effect and grain refining effect. The main wear mechanism of
nano-composite coating is abrasive wear, the wear mechanism of magnesium alloys is adhesion wear, and that of pure nickel coating
is exfoliation wear, respectively.
Key words: magnesium alloy; nano-composite coatings; microstructure; wear resistance

conversion coating [4−5], anodizing [6−9], micro-arc

1 Introduction
Magnesium alloy has many prominent characters
such as high strength (stiffness) radio, electromagnetic
shielding, vibration abatement, superior cutting
performance and recoverability. In recent years,
magnesium alloy has been developed quickly in the
industrialization. Especially, magnesium alloy was
applied in aerospace, automotive industry and electronic
communications. AZ91HP magnesium alloy has
excellent performances of casting process and low-cost,
which has become the most widely used casting
magnesium alloy. Magnesium has a negative standard
potential, so that magnesium alloy is poor corrosion
resistant [1]. On the other hand, the hardness of
magnesium alloy is low, so that the wear resistance is
poor also. Therefore, the application of magnesium alloy
is restricted [2]. To improve the properties of magnesium
alloy, many surface modification technologies were used,
including electroplating, electroless plating [3],
oxidation [10], hydride coating [11], organic/polymer
coatings [12−13] and gas phase deposition [14−16].
Especially, the micro-arc oxidation technology,
compared with ordinary anodic oxidation, has
advantages such as process simple, pollution-free,
uniform coating as well as wide materials adaptability,
and has become the main protective technology of
magnesium alloy. In recent years, the nano-composite
electrodeposition technology was used to fabricate new
types of nano-composite coating of magnesium alloy
[17−18].
In this work, the nano-composite coatings were
prepared by composite electrodeposition, and the
microstructure and wear resistance were discussed.
2 Experimental
Fabrication process of nano-composite coating was
designed as follows: sample preparation — alkaline
cleaning—pickling—activating—electroless plating—

Foundation item: Project (50905071) supported by the National Natural Science Foundation of China; Project (20090539) supported by the Program for the
Development of Science and Technology of Jilin Province, China; Project (20100471247) supported by the Postdoctoral Science
Foundation of China
Corresponding author: LIU Yan; Tel: +86-431-85095760; E-mail: liuyan2000@jlu.edu.cn
s484 LIU Yan, et al/Trans. Nonferrous Met. Soc. China 21(2011) s483−s488
nano-composites electrodeposition. After each step, the
sample must be washed with water for 1 min to remove
the residual liquid of the last process and avoid affecting
next process.
AZ91HP magnesium alloy samples with size of 55
mm × 10 mm × 10 mm were cut by electro-discharge
(DK7732E). The samples were ground with sandpaper to
remove the surface oxide film and other impurities.
Electro- deposition equipments were SMD-30 Numerical
Control Double Pulse Plating Power Supply, KQ−250DE
Numerical Control Ultrasonic Devices and JJ−1 Electric
Mixing Machine.
Nano-particles have a very high surface energy and
great specific surface area, so are easy to aggregate
reunion in the electrolyte. Therefore, nanoparticles
aggregation must be effectively solved in the fabrication
process. To obtain high dispersion of nanoparticles in the
electrolyte, a small amount of dispersing agent was used
to fully wet n-SiO2 at first, then was ultrasonic oscillated
for more than 4 h, at was last added in the electrolyte.
The ultrasonic oscillation and mechanical mixing were
used together in the electrodeposition process. The
component and parameters of pretreatment bath were
listed in Table 1 and the electrodeposition parameters of
preparing Ni-SiO2 composite coating were listed in Table
2.
decrease due to the dimension effect of nanoparticles
(Fig. 1). The high active surface of nanoparticles
provides an amount of nucleus for Ni atoms in the
process of electrodeposition. The overpotential of metal
forming nucleus reaction decreases. The composite
coating with fine and compact microstructure is obtained
because of the higher nucleation rate [19]. On the other
hand, in the coating deposition process, the nickel
polycrystalline modules of predeposition form the
microscopic nodular and the phenomenon results in
“edge effect”, so that the current density increases and
deposition rate accelerates, in which the role of feedback
loop is produced. The “edge effect” would be hindered
due to the diffusion deposition of nano-particles on the
coating surface in the electrodeposition process.
Moreover, the consecutive growth of nickel metal in the
nano-particles deposited position is impeded, so that the
crystal plane orientation of original nickel grain occurs to
change and turns to new epitaxial growth. With the
nano-particles of composite coatings increasing, the
nickel crystal plane orientation becomes more littery. The
epitaxial growth of nickel grain to larger sizes is
impossible in a certain crystal plane orientation, so that
the grains of nickel become fine. Therefore, when the
surface of AZ91HP magnesium alloy electrodeposition

Table 1 Component and parameter of pretreatment bath

Component Value/(g·L−1) Parameter Value
NaSiO4·6H2O 15 pH 6.4
NaH2PO2·H2O 14 Temperature/°C 82±2
NaC2H3O2 13
HF (40%) 12
NH4HF2 8
Stabilizer 0.001

Table 2 Electrodeposition parameters of preparing Ni-SiO2

composite coating
Component Value/(g·L−1) Parameter Value
NaSiO4·6H2O 280 Current density/
20−80
NiCl2·6H2O 40 (mA·mm−2)
H3BO3 35 pH 3.5−4.5
Wetting agent 0.1−0.2 Temperature/°C 50−60
Dispersant 0.1−0.5

3 Results and discussion

3.1 Microstructure of Ni-SiO2 composite coatings on

AZ91HP magnesium alloy surface
Compared with the Ni coating, the sizes of crystal Fig. 1 Microstructures of coating on AZ91HP magnesium alloy:
grains in the Ni-SiO2 nanocomposite coating largely (a) Pure nickel coating; (b) Ni-SiO2 nano-composite coating
 LIU Yan, et al/Trans. Nonferrous Met. Soc. China 21(2011) s483−s488
coating was compared to that of the pure nickel, the
crystallization of nanocompostie coatings is more
uniform and denser.
Figure 2 shows the interface of AZ91HP
magnesium alloy and Ni-SiO2 nano-composite coating
by SEM. The nano-composite coating is even, compact,
with no obvious cracks, holes, and so on. The thickness
of composite coating is about 20 μm. The combination
between the composite coatings and AZ91HP
magnesium alloy is very well.
Fig. 2 Interface morphology of Ni-SiO2 nano-composite
coating
3.2 Microhardness of Ni-SiO2 composite coating on
AZ91HP magnesium alloy surface
Figure 3 shows the microhardness of Ni-SiO2 nano-
composite coating with different concentration of n-SiO2
in the electrodeposition bath. The maximum
microhardness is HV367 when the content of n-SiO2 is
10 g/L. The reasons are that the nanoparticles have a
dispersion strengthening effect, which impede the
dislocation movement of metallic matrix and limit grain
boundary sliding. Therefore, the microhardness of the
composite coatings is enhanced. On the other hand, the
nanoparticles as new growth points make the growth rate
of the crystal nucleation decrease, which leads to the
Fig. 3 Microhardness of Ni-SiO2 nano-composite coatings
s485
grain refinement. Therefore, the mechanical properties of
composite coating are also improved. Usually, the
amount of n-SiO2 suspended in the electrodeposition
bath increase with the content of nanoparticles increasing.
At the same time, the amount of nanoparticles contained
in the coating increases. However, when the content of
the nanoparticles increases to a certain extent, the very
small nanoparticles are prone to agglomeration due to the
specific surface area effect, resulting in the increase of
solution viscosity, and hindering the movement of matrix
metal plasma so that the deposition rate decreases.
Therefore, when the content of nanoparticles in the
electrodeposition is high enough, the nanoparticles of
composite coating will decrease.
3.3 Wear resistance of Ni-SiO2 composite coatings on
AZ91HP magnesium alloy surface
Figure 4 shows the wear morphologies of AZ91HP
magnesium alloy, pure nickel coating and nanocomposite
coating at low load, respectively. Figure 5 shows the
wear morphologies of AZ91HP magnesium alloy, pure
nickel coating and nanocomposite coating at high load,
respectively. It can be seen that, the wear mechanism of
AZ91HP magnesium alloy surface is mainly adhesive
wear. In low-load (10 N) wear, the friction pairs generate
plowing on the substrate surface (Fig. 4(a)). With the
load (30 N) increasing, the plowing is deepened and
widened on the surface of AZ91HP magnesium alloy.
The material surface generates elasto-plastic deformation,
accompanied with repeated plastic deformation, leading
to surface cracks. With the friction continuing, the
temperature gradually increases, and the surface
adhesion wear becomes obvious. These adhesive friction
points have been cut in the friction course, thus form
adhesive wear (Fig. 5(a)).
The wear surface of the pure nickel coating at
low-load (10 N) is flat, but there are some grooves
parallel to the direction of friction pairs movement and
the grooves are shallow (Fig. 4(b)). In sliding wear
process, the interface parts will be the first occurrence of
fatigue damage due to repeated shear stress. When the
accumulation of fatigue damage reaches to a certain
extent, the microcracks are formed. The macrocracks are
formed due to the microcracks expanding and connection
under cyclic stress. At the same time, these macrocracks
expand toward the material weakness. With the load
(30 N) increasing, the macrocracks expand continually.
When the intensity factor (Kmax) of the crack tip stress is
gradually close to the material fracture toughness (Kc),
the cracks will occur with a sharp local buckling, which
behave as being cut (Fig. 5(b)). Therefore, large areas
exfoliation occur at the cracks parts of the pure nickel
coating [20], which is a typical exfoliation wear.
The wear surface of nano-composite coating is not
s486 LIU Yan, et al/Trans. Nonferrous Met. Soc. China 21(2011) s483−s488
Fig. 4 Wear surface morphologies at low load (10 N):
(a) Magnesium alloy; (b) Pure nickel coating; (c) Nano-
composite coating
only flat at low-load (10 N), but also grooved parallel to
the direction of friction pairs movement, and the grooves
are shallow, which are similar to pure nickel coating. But
the amount of cracks is less than that of pure nickel
coating obviously (Fig. 4(c)). With the load (30 N)
increasing, grooves are deepened on the wear surface of
composite coating and appear small wear debris. But
there are no large areas exfoliation phenomenon, and
wear debris will be involved in the wear process, where
wear mechanism is a typical abrasive wear (Fig. 5(c)).
Therefore, the wear resistance of composite coating is
improved obviously. The main reasons are nanoparticulate
grain refining and dispersive strengthening effects. The
Fig. 5 Wear surface morphologies at high load (30 N):
(a) Magnesium alloy; (b) Pure nickel coating; (c) Nano-
composite costing
nanoparticles uniformly distribute in the composite
coating, and serious distortion occurs near the
nanoparticles. At the same time, the defects increase, the
nickel matrix dislocations movement and deformation
are hindered. Therefore, the hardness and strength of the
coatings significantly increase [21−23]. In the friction
process, the nanoparticles embedded in the composite
coating are exposed gradually in the contact surface, and
play a load-bearing role, which inhibit the expansion and
peeling of the adhesion areas and strengthen the adhesive
wear resistance [24−26]. The wear mechanism of
nanocomposite coating is abrasive wear, which is
superior to wear resistance of pure nickel coating.
 LIU Yan, et al/Trans. Nonferrous Met. Soc. China 21(2011) s483−s488
4 Conclusions
1) Sulfate salts were used as pretreatment of
electroless plating process. Electrodeposition was used to
fabricate Ni-SiO2 nanocomposite coatings on the
AZ91HP magnesium alloy.
2) The Ni-SiO2 nanocomposite coatings with
uniform crystalline, dense structure are obtained on the
AZ91HP magnesium alloy. The interface morphology
shows that the combination between the nanocomposite
coatings and magnesium alloy is fine.
3) The maximum value of microhardness reaches
HV367 when the content of nanoparticles is 10 g/L,
which is higher than that of pure nickel coatings and
magnesium alloy. The frication and wear experiments
reveal that the wear resistance of nanocomposite coatings
are improved obviously compared to the magnesium
alloys and pure nickel coatings, which are induced by
dispersive strengthening effect and grain refining effect.
The main wear mechanism of nanocomposite coating is
abrasive wear, the wear mechanism of magnesium alloys
is adhesion wear, and that of pure nickel coating is
exfoliation wear, respectively.
References
[1] MATHIEU S, RAPIN C, STEINMETZ J, et al. A corrosion study of
the main constituent phases of AZ91 magnesium alloys [J].
Corrosion Science, 2003, 45(12): 2741−2755.
[2] GAO Fu-qi, GAO Bing, GAO Xiang. Electroplating technology for
surface of magnesium alloy [J]. Surface Technology, 2004, 30(1):
8−10. (in Chinese)
[3] HE Y D, FU H F, LI X G, GAO W. Microstructure and properties of
mechanical attrition enhanced electroless Ni-P platings
magnesium alloy [J]. Scripta Materialia, 2008, 58(6): 504−507.
[4] HIROYUKI U. An investigation of the structure and corrosion
resistance of a permanganate conversion coating on AZ91D
magnesium alloys [J]. Materials Transactions, 2001, 42(8): 1691−
1699.
[5] RUDD A L, BRESLIN C B, MANSFELD. The corrosion protection
afforded by rare earth conversion coatings applied to magnesium [J].
Corrosion Science, 2000, 42(2): 275−288.
[6] KHASELEV O, WEISS D, YAHALOM J. Structure and composition
of anodic film formed on binary Mg-Al Alloys in KOH—Aluminate
solution under continuous sparking [M]. Corrosion Science, 2001,
43(7): 1295−1307.
[7] ONO S, KIJIMA J, MASUKO N. Microstructure and voltage−
current characteristics of anodic films for magnesium in electrolytes
containing fluoride [J]. Materials Transactions, 2003, 44(4): 539−
545.
[8] BRCHICHE C E, ROCCA E, JUERS C, HAZAN J, STEINMETZ J.
Corrosion resistance of plasma-anodized AZ91D magnesium alloy
by electrochemical methods [J]. Electrochimica Acta, 2007, 53(2):
417−425.
[9] WEN C S, CHIEN C C, SHENG J H. Electrochemical
s487
characterization of non-chromate surface treatments on AZ80
magnesium [J]. Material Characterization, 2008, 59(10): 1400−1406.
[10] ZHI Q, GAO J, DONG C F, LI X G. Corrosion behavior of microarc
oxidation film on AZ91D magnesium alloy [J]. Acta Metallurgica
Sinica, 2008, 44(8): 986−990. (in Chinese)
[11] NAKATSUGAWA I. Cathodic protective coating on magnesium or
its alloys and method of producing the same alloys. US 6117298 [P].
2000.
[12] TRUONG V T, LAI P K, MOORE B T. Corrosion protection on
magnesium by electroactive polypyrrole/paint coatings [J]. Synthetic
Metals, 2000, 110(1): 7−15.
[13] LI Q, ZHONG X K, HU J Y, WEI K. Preparation and corrosion
resistance studies of zirconia coating on fluorinated AZ91D
magnesium alloy [J]. Progress in Organic Coatings, 2008, 63(2):
222−227.
[14] HOLLSTEIN I, WIEDMANN R, SCHOLZ J. Characteristics of
PVD-coatings on AZ31HP magnesium alloys [J]. Surface and
Coating Technology, 2003, 162(2−3): 261−268.
[15] GRAY J E, LUAN B. Protective coatings on magnesium and its
alloys—a critical review [J]. J Alloys Compd, 2002, 336(1−2):
88−113.
[16] HIKMET A, HAKAN S. Corrosion behaviour of magnesium alloys
coated with TIN by cathodic arc deposition in NaCl and Na2SO4
solutions [J]. Materials Characterization, 2008, 59: 266−270.
[17] LI Q, ZHONG X K, ZHANG L, WANG J P, CHEN B. Corrosion
resistance and mechanical properties of pulse electrodeposited
Ni-TiO2 composite coating for sintered NdFeB magnet [J]. J Alloys
Compd, 2009, 482(1−2): 339−344.
[18] CHEN L, WANG L P, ZENG Z H, ZHANG J Y. Effect of surfactant
on the electrodeposition and wear resistance of Ni-Al2O3 composite
coatings [J]. Mater Sci Eng A, 2006, 434: 319−325.
[19] DU L Z, XU B S, DONG S Y. Study of tribological characteristics
and wear mechanism of nano-particle strengthened nickel-based
composite coatings under abrasive contaminant lubrication [J]. Wear,
2004, 257: 1058−1063.
[20] ZHU Zi-xin, XU Bing-shi, ZHENG Jing, et al. High velocity arc
on
spraying wear exfoliation model [C]// The Sixth Conference of
Surface Technology. Lanzhou, 2006: 645−647. (in Chinese)
[21] WANG L Y, TU J P, CHEN W X. Friction and wear behavior of
electroless Ni-based CNT composite coatings [J]. Wear, 2003,
254(12): 1289−1293.
[22] XU Yu-jun, ZHU Di, JIN Guang-hu, et al. Friction and wear
properties of electrodeposited Ni-La2O3 nanocomposite coatings [J].
Tribology, 2005, 25(1): 1−6. (in Chinese)
[23] LEE W, TANG S, CHUNG K. Effects of direct current and
pulse-coating on the co-deposition of nickel and nanometer diamond
powder [J]. Surface and Coatings Technology, 1999, 120−121:
607−611.
[24] SHI L, SUN C F, ZHOU F, et al. Electrodeposited nickel-cobalt
composite coating containing nano-sized Si3N4 [J]. Materials Science
and Engineering A, 2005, 397(1−2): 190−194.
[25] WANG W, HOU F Y, WANG H. Fabrication and characterization of
Ni-ZrO2 composite nano-coatings by pulse electrodeposition [J].
Scripta Materialia, 2005, 53(5): 613−618.
[26] CHEN X H, CHEN C S, XIAO H N. Corrosion behavior of carbon
nanotubes-Ni composite coating [J]. Surface and Coatings
Technology, 2005, 191(2−3): 351−356.
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AZ91HP 镁合金电沉积 Ni-SiO2 纳米复合镀层的

显微结构与耐磨性
刘 燕 1, 于思荣 2，刘金丹 1，韩志武 1，苑东生 2

1. 吉林大学 工程仿生教育部重点实验室，长春 130022;

2. 吉林大学 材料科学与工程学院，长春 130022

摘 要：以 AZ91HP 镁合金为研究对象，以纳米氧化硅为第二相粒子，通过纳米复合电沉积法制备 AZ91HP 镁

合金 Ni-SiO2 纳米复合镀层。利用扫描电镜观察纳米复合镀层的显微形貌与微观结构，利用显微硬度计测定纳米
复合镀层显微硬度，利用 M−200 摩擦磨损试验机测试纳米复合镀层的耐磨性能。结果表明：在 AZ91HP 镁合金
表面获得了结晶均匀、结构致密的 Ni-SiO2 纳米复合镀层；纳米复合镀层剖面形貌显示纳米复合镀层与镁合金基
体结合良好；镀液中纳米颗粒含量为 10 g/L 时，AZ91HP 镁合金表面电沉积 Ni-SiO2 纳米复合镀层的显微硬度最
高，最高达 HV367；摩擦磨损试验表明纳米复合镀层与镀镍层、镁合金基体相比，耐磨性明显提高，这是由于纳
米颗粒的细晶强化和弥散强化所致；纳米复合镀层的磨损机制主要是磨粒磨损，镁合金基体磨损机制为粘着磨损，
镀镍层磨损机制为剥层磨损。
关键词：镁合金；纳米复合镀层；显微结构；耐磨性
(Edited by LONG Huai-zhong)